CN104768990B - The reactive fluid rubber being made up of the isocyanate-terminated prepolymer closed with glycol capturing agent - Google Patents

Abstract

The method that the present invention describes the liquid rubber for preparing the impact modifier blocked comprising epoxide group, methods described includes making isocyanate-terminated prepolymer and reacted comprising the epoxy resin with primary hydroxyl or the epoxides of secondary hydroxyl in the presence of the compound selected from acid anhydrides, ketone and aldehyde (as glycol capturing agent), isocyanate-terminated prepolymer, epoxy resin and glycol capturing agent is mixed with each other or react epoxy resin and glycol capturing agent, it is mixed with isocyanate-terminated prepolymer.The gel in reactant mixture is avoided by methods described.The product obtained is suitable for improving the impact flexibility of composition epoxy resin, particularly one-component or bicomponent epoxy resin adhesive.

Description

The reactivity being made up of the isocyanate-terminated prepolymer closed with glycol capturing agent Liquid rubber

Technical field

The present invention relates to the method for the liquid rubber for preparing the impact modifier blocked comprising epoxide group, by described The liquid rubber that method is obtained, the purposes of the liquid rubber and the one-component comprising the liquid rubber or two component epoxy tree Oil/fat composition, the composition epoxy resin is preferably adhesive.

Background technology

In the manufacture of vehicle and annex or machine and instrument, instead of conventional bonding methods (for example bolt connection, riveting, Punching press or welding) or combine with conventional bonding methods, more and more using senior adhesive.Therefore manufacturing (such as multiple The manufacture of condensation material and hybrid materials) in bigger free degree when forming advantage and new possibility or component design.For It is used in vehicle production, adhesive must be in all used substrates (particularly electrogalvanising, galvanizing and subsequent phosphorus The steel plate of change, oiling steel plate) on and there is in optional surface treated different aluminum alloys good adhesiveness.Especially Ground, after aging (alternation weather, salt fog bath etc.), the good adhesion property must keep and be damaged without big quality Lose.When adhesive is used as the white body adhesive in automobile making, described adhesive is relative to rinse bath and immersion coating Tolerance (so-called washability) is significant, so as to ensure the process safety of the producer.

In the case of single-component adhesive, the adhesive for white body should be ideally at 30 minutes and 180 DEG C Solidify under usual baking condition.In the case of two-component adhesive, solidification should be at room temperature in the time of a couple of days to about 1 week It is interior to carry out, but the solidification pattern of acceleration can also be used, such as at room temperature 4 hours then 30 points at 60 DEG C or 85 DEG C Clock.In addition, adhesive should also up to about 220 DEG C be stable.To the cured adhesive or other requirements of bonding Be ensure up to about 90 DEG C high temperature and it is minimum of about -40 DEG C in a low temperature of processing safety.Due to these bondings Agent is construction adhesive and therefore these adhesive bonding structure members, so the high intensity and impact flexibility of adhesive have Significance.

Although the feature of Conventional epoxy compound adhesive is high mechanical strength, particularly high tensile strength.But In the case where bonding is by unexpected load, Conventional epoxy compound adhesive is most excessively crisp and is therefore born in the big stretching of appearance Required under the impact conditions of lotus and peel load far from satisfaction, the particularly requirement of auto industry.Thus, in high temperature Under, but particularly in low temperature (for example<- 10 DEG C) under intensity it is especially not enough.

Pass through the fragility and the therefore method of rise impact toughness of two kinds of reduction epoxides adhesives known to document：One Aspect can be by blending the high-molecular weight compounds (such as the core shell polymer or other toughening polymers that are at least partly crosslinked With the latex of copolymer) so as to realize the purpose.Such a method is for example described in US 5290857.On the other hand It can realize that certain toughness is raised by introducing soft chain segment (such as by the corresponding modification of epoxide component).For example Describe composition epoxy resin in US 4952645, the composition epoxy resin by with carboxylic acid, particularly dimerization or Trimerized fatty acids and with carboxylic acid-terminated diol reaction so as to carrying out toughness reinforcing.

The A2 of EP 0353190 are related to the toughness reinforcing group for the epoxy resin based on single phenol end-blocking or epoxy-capped polymer Point.The A1 of EP 1574537 and the A1 of EP 1602702 describe epoxy adhesive composition, the epobond epoxyn Composition includes single phenol end-blocking or epoxy-capped polymer is used as anti-impact agent.

The A1 of WO 2004/055092 are described to be changed by the anti-impact blocked in epoxides adhesive using epoxide group Property agent so as to improved impact flexibility heat-setting composition epoxy resin, wherein the impact modifier pass through it is different The prepolymer of cyanate end-blocking is obtained with the reaction of hydroxy-end capped epoxide.

The A1 of WO 2005/007720 describe the impact modifier of epoxide group end-blocking, and the impact modifier passes through different The prepolymer of cyanate end-blocking is obtained with the reaction of hydroxy-end capped epoxide, wherein the impact modifier has at least A kind of aromatic structure unit, the aromatic structure unit is combined in polymer chain by carbamate groups.

Epoxy composite is described in the A1 of US 2009/0029059, the epoxy composite is suitable for coating water pipe.Institute State composition and include epoxy resin, acid anhydrides and curing agent.Double-salmefamol, institute is included in used composition epoxy resin Double-salmefamol is stated without epoxide group and matrix is not therefore reacted into.For this reason, double-salmefamol can be from painting Washed out in layer, this causes health problem.Therefore a kind of method is also described, double-salmefamol present in its epoxy resin leads to Cross and converted with anhydride reaction, so as to substrate reaction.

The A of FR 1531824 are related to react with epoxy alcohol by the polyurethane of isocyanate-functional to be aoxidized so as to prepare polycyclic Thing.Can then be made to be obtained with curing agent (such as acid anhydrides) is product solidified.

EP 1916272 A1, EP 1431325 the A1 and A1 of EP 1498441 describe comprising epoxide group block it is poly- The composition of urethane prepolymer, the polyurethane prepolymer is by the polyurethane prepolymer comprising isocyanate groups and includes hydroxyl The reaction of the epoxide of base is obtained.

The impact modifier blocked by using epoxide group is (such as in the above-mentioned A1 of WO 2004/055092 or WO Those described in 2005/007720 A1), it can realize and significantly improve in one-component or bicomponent epoxy resin adhesive Impact flexibility.As the accessory substance or preferably pointedly of synthesis, many epoxy resin, which are included, has primary hydroxyl or secondary hydroxyl The epoxide of base.It is desirable that, formed by the reaction of isocyanate-terminated prepolymer and the epoxy resin The impact modifier of epoxides end-blocking.

But in the synthesis of epoxy resin, a large amount of epoxidations as accessory substance are also formed in addition to target compound Thing and glycol.Although need not separate these accessory substances to prepare reactive fluid rubber, but its residual in system is limited The freedom of further preparation is made, because as submember comprising glycol in the epoxy due to its elevated degree of functionality It is likely to result in the impact modifier gelation of epoxy resin end-blocking.Guess the material containing OH of difunctionality and/or be particularly reactivity Material containing OH, the list-salmefamol included especially as submember tackled in asphalt mixtures modified by epoxy resin due to its elevated degree of functionality Gelation is responsible for what is observed in the impact modifier of fat end-blocking.

Therefore, the preparation of the impact modifier of the epoxide group end-blocking based on epoxy resin typically results in the gel of polymer Change and inhomogeneities so that processing difficulties.

The content of the invention

It is an object of the invention to provide the impact modifier for composition epoxy resin, the impact modifier does not have The problem of gelation and formation inhomogeneities, so as to thus raise process safety.The impact modifier should be preferably adapted for It is used as one-component or the composition of bicomponent epoxy resin composition, particularly adhesive.

Unexpectedly, can by the method for the liquid rubber for preparing the impact modifier blocked comprising epoxide group To realize the purpose, methods described includes making the isocyanate-terminated prepolymer of formula (II) with epoxy resin at least one Reacted in the presence of the compound as glycol capturing agent selected from acid anhydrides, ketone and aldehyde

Wherein X₁=O, S or NH；

Y₁Represent n valency group of the reactive polymer after amino, sulfydryl or the hydroxyl of end is removed；

Y₂Represent the divalence of aliphatic, alicyclic, aromatics or araliphatic diisocyanate after isocyanate groups are removed Group, or represent that the trimer or biuret of aliphatic, alicyclic, aromatics or araliphatic diisocyanate are removing isocyanates Trivalent radical after group；

M=1 or 2；With

N=2,3 or 4；It is preferred that 2 or 3,

The epoxide with primary hydroxyl or secondary hydroxyl of the epoxy resin comprising formula (III),

Wherein Y₃Represent removing comprising primary hydroxyl or the aliphatic, alicyclic of secondary hydroxyl, aromatics or araliphatic epoxides Group after epoxide group and primary hydroxyl or secondary hydroxyl；With

Q=1,2 or 3；

The isocyanate-terminated prepolymer, epoxy resin and glycol capturing agent of formula (II) is wherein set to be mixed with each other or make Epoxy resin reacts with glycol capturing agent, it is mixed with the isocyanate-terminated prepolymer of formula (II).

Glycol capturing agent in theory can with all possible radical reaction in epoxy resin (OH, epoxides), and Extraly with being reacted to solidify used amine in the adhesive formulation of completion, and therefore cause a large amount of possible things Matter.Therefore it was unexpectedly determined that glycol capturing agent optionally only closes the glycol included in epoxy resin, this causes first This preparation is feasible in technology.

Prepolymer is oligomeric compound or aggregated compound itself, and it is served as synthesizing high molecular weight material Raw material or intermediate product.Prefix " poly-/many " in term (such as polyalcohol or polyisocyanates) represents that compound has two Or more the group, therefore polyalcohol is the compound with two or more hydroxyls.

The impact modifier that one or more epoxide groups are blocked is included according to liquid rubber produced by the present invention.Liquid rubber Glue is reactive fluid rubber.The impact modifier of epoxide group end-blocking includes completely enclosed or partially enclosed isocyanates envelope The prepolymer at end.Isocyanate-terminated prepolymer is also referred to as PU- polymer herein.

The isocyanate-terminated prepolymer or PU- polymer of used formula (II) carry X to be one or more₁H- bases The compound of group and the reaction product of one or more polyisocyanates.Reaction can enter in one or more steps OK.The isocyanate-terminated prepolymer of used formula (II) can be, for example, to carry X₁The compound of the formula (IV) of H- groups With the reaction product of the polyisocyanates of formula (V), wherein substituent and index to be defined with identical mode in formula (II).

The compound of formula (IV) has group X₁H.The group X₁H can be OH, SH or NH independently of one another₂.Preferred amines Base and hydroxyl, wherein particularly preferred hydroxyl.With X₁The compound of the formula (IV) of H- groups can be prepolymer or polymer.

It is preferred that formula (IV) compound be polyalcohol, such as following commercial polyols or its any mixture：

Polyoxyalkylene polyols (also referred to as PPG), it is oxirane, 1,2- expoxy propane, 1,2- Or 2,3- epoxy butanes, tetrahydrofuran or the optional of its mixture are divided by means of the starting with two or three active hydrogen atoms The polymerizate of son polymerization, the starting molecule is, for example, water or the compound rolled into a ball with two or three OH-groups.It can use For example there is low-unsaturation-degree (root by means of prepared by so-called bimetallic cyanide complex catalyst (abbreviation DMC- catalyst) According to ASTM D-2849-69 measure and with milliequivalent degree of unsaturation/gram polyalcohol () represent) and polyoxyalkyl Polylol, can also use the tool for example prepared by means of anionic catalyst (such as NaOH, KOH or alkali metal alcoholates) There are the polyoxyalkylene polyols of higher degree of unsaturation.It is specially suitable to be less than particularly to have Degree of unsaturation and/or the molecular weight in the range of 1000 to 30000g/mol oxide glycols and polyoxygenated Asia third Base triol, polyoxybutylene glycol and polyoxybutylene triol with particularly 400 to 8000g/mol molecular weight, Oxide glycols and polyoxypropylene triol, and so-called " EO- end-blockings " (have oxirane end group) it is poly- Oxypropylene glycol or polyoxypropylene triol.The latter is specific polyoxypropylene polyoxyethylene polyols, It is for example achieved in that：With the polyoxypropylene polyol that oxirane alkoxylate is pure after poly- propoxylation terminates, And therefore make it have primary hydroxyl；

For example by dihydric alcohol to trihydroxylic alcohol (such as 1,2- ethylene glycol, diethylene glycol, 1,2- propane diols, DPG, 1,4- Butanediol, 1,5- pentanediols, 1,6-HD, neopentyl glycol, glycerine, the mixing of 1,1,1- trimethylolpropanes or above-mentioned alcohol Thing) and organic dicarboxylic acid or its acid anhydrides or ester (such as butanedioic acid, glutaric acid, adipic acid, suberic acid, decanedioic acid, dodecane dicarboxyl Acid, maleic acid, fumaric acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA) and hexahydrophthalic acid are above-mentioned sour mixed Compound) made from PEPA, and the PEPA derived from lactone such as 6-caprolactone；With

Polycarbonate polyol, as example, by it is above-mentioned for synthesizing polyester polyalcohol used in alcohol and dialkyl carbonate Those of the reaction acquisition of ester, diaryl carbonate or phosgene.

Advantageously, with X₁The compound of the formula (IV) of H- groups be OH- equivalent weights be 600 to 6000g/OH- equivalents, It is preferred that 700 to 2200g/OH- equivalents difunctionality or the polyalcohol of higher functional.It is further advantageous that polyalcohol is selected from poly- second two It is alcohol, polypropylene glycol, polyethylene glycol propane diols-block polymer, polytetramethylene glycol, hydroxy-end capped polybutadiene, hydroxy-end capped Butadiene-co-acrylonitrile, the mixture of hydroxy-end capped synthetic rubber and the polyalcohol.

Polyvinylether, polypropylene ether, polybutene ether, polybutadiene that the amine of difunctionality or higher functional blocks can also be used Alkene, Polybutadiene-acrylonitrile and other amine end-blocking synthetic rubber or the component mixture as formula (IV) chemical combination Thing.Particularly preferably for example with two, three or four amine-terminated polyetheramines (for example)。

Compound particularly preferable as formula (IV) is with C₂-C₆- alkylidene or the C with mixing₂-C₆- alkylidene Use amino, sulfydryl or hydroxyl (preferably hydroxyl) end-blocking α, ω-PAG.Particularly preferably polyether polyol Such as the polyethers of hydroxy-end capped polyoxybutylene and polypropylene glycol, hydroxy-end capped polybutadiene and amine end-blocking.

In a preferred embodiment, using being used as at least two, preferably two or three of formula (IV) compound Formula (IV) have X₁The mixture of H=OH compound, i.e., the rubber that at least one PPG is blocked with least one OH- Glue is combined, and wherein the part by weight for the rubber that PPG and OH- are blocked is preferably 7:3 to 2:In the range of 8.Therefore can be with Improve mechanical performance.The rubber of PPG and OH- end-blockings is as described above.Be described below PPG and OH- end-blocking Rubber, it is particularly suitable for the combination, but can also optionally be used alone.

One or more PPGs can be used.Particularly preferred PPG is oxirane, 1,2- epoxies The polymerizate of propane, 1,2- or 2,3- epoxy butane, tetrahydrofuran or its mixture, particularly preferably PPOX and poly- Tetrahydrofuran.These PPGs are commercially available.The PolyTHF of commercially available acquisition is such as BASF's - product, for example2000、2500CO or3000CO.Commercially available acquisition it is poly- Expoxy propane is such as Shell's- product, for example2000 orED56, or Bayer's- product, for example-Polyol2200、- Polyol 12200 or-Polyol 4200.Other possible PPGs are Dow's1010L、 EP1900 orCP4755。

The mean molecule quantity of used PPG can change.PPG have for example 500 to In the range of 5000g/mol, preferably 1000 to 3000g/mol, particularly preferably in the range of 1500 to 2500g/mol, particularly from about 2000g/mol weight average molecular weight (Mw).

If not stated otherwise, weight average molecular weight is determined by GPC method in this application.GPC method is liquid phase color One kind of spectrometry, wherein different size of molecule is separated due to its different diffusion volume.Therefore, according to polymerization to be determined Thing uses different splitters：Post：SDV 100,1000,(0.8x 30cm, 5 μm)；Eluent：THF；Flow： 1mL/min；Temperature：35℃；Relative to the correction of poly- (1,4- butadiene)-standard specimen：831–1060000g/mol；Preparation of samples：Will About 100mg samples are dissolved in 10mL THF and filtered with 0.45 μm of PTFE- membrane filters.

The OH- degrees of functionality of used PPG preferably in the range of about 2, for example 1.9 to 2.1 scope It is interior.It is optionally possible to be mixed into the compound that OH- degrees of functionality are 3, such as butoxylated trihydroxy methyl third in PPG Alkane is (for exampleTOMB), so as to raise OH- degrees of functionality.

Titrimetry OH- degrees of functionality can for example be passed through.Material comprising hydroxyl and excessive di-isocyanate reaction are simultaneously And the isocyanates of excess is determined in the way of titrating by means of 0.1M HCl solutions after reacting and hydroxyl value is calculated.

The rubber that one or more OH- can be used to block, wherein using the rubber of two kinds of OH- end-blockings, particularly two kinds The polybutadiene of OH- end-blockings, causes particularly advantageous performance.OH- end-blocking rubber be herein understood to for example with preferred hydroxyl The polybutadiene of end-blocking and the polyalcohol based on castor oil, wherein hydroxy-end capped polybutadiene is particularly preferred.Castor oil For triglyceride, its hydroxyl of OH- degrees of functionality based on castor oil acid, and be therefore polyalcohol.Castor oil is can be different The natural products that quality (such as using standard quality, as dehydration product or with extremely low acid number) is obtained.Derivative can also be obtained The castor oil of the castor oil product of change, such as oxidation polymerization or partially dehydrated castor oil, can for example be adjusted by them Relatively low OH- degrees of functionality.Polyalcohol based on castor oil includes the castor oil and castor oil derivative of different qualities.

The hydroxy-end capped polybutadiene of commercially available acquisition is such as Cray Valley Poly- product and- product, for exampleLBH-P 2000 or PolyR45V.Exemplified by polyalcohol based on castor oil Such as Alberdingk Boley- product, for example901, or Baker Castor Oil Company's- product, for example-GR80。

Used hydroxy-end capped rubber preferably has less than 15000g/mol, and preferably smaller than 4000g/mol weight is equal Molecular weight (Mw).

The OH- degrees of functionality of used hydroxy-end capped rubber are preferably in the range of 1.7 to 2.2 (for anion system Type) or in the range of 2.2 to 2.8 (for type made from free radical).When epoxide group block it is impact-resistant modified When agent is used in bicomponent epoxy resin adhesive, the hydroxy-end capped rubber that OH- degrees of functionality are less than or equal to 2 is preferably used, it is special It is not hydroxy-end capped butadiene.When the impact modifier that epoxide group is blocked is used in single component epoxy adhesive, Preferably use hydroxy-end capped rubber of the OH- degrees of functionality in the range of 2.4 to 2.8, particularly hydroxy-end capped butadiene.It is described Can also be special in two kinds of hydroxy-end capped rubber for the preferred OH- degrees of functionality of two-component and single component epoxy adhesive Realized in the case of the mixture for not being hydroxy-end capped butadiene.

The part by weight of PPG and hydroxy-end capped rubber is preferably 7:3 to 2:8th, preferably 7:3 to 4:6 and especially It is preferred that 7:3 to 5:In the range of 5.The mechanical performance of cured adhesive can be improved in this way, particularly at -30 DEG C Under impact peel work(.

Isocyanate-terminated prepolymer passes through with X₁H compound and the reaction of polyisocyanates are obtained.Suitably The polyisocyanates of formula (V) is diisocyanate or triisocyanate.Suitable diisocyanate is aliphatic, alicyclic, aromatics Or araliphatic diisocyanate, particularly commercially available prod such as methylenediphenyl diisocyanates (MDI), hexa-methylene two are different Cyanate (HDI), toluene di-isocyanate(TDI) (TDI), tolidine diisocyanate (TODI), IPDI (IPDI), trimethyl hexamethylene diisocyanate (TMDI), 2,5- or 2,6- double-(isocyanatometyls)-are bicyclic [2.2.1] Heptane, 1,5- naphthalene diisocyanates (NDI), dicyclohexylmethyl diisocyanate (H₁₂MDI), p-phenylene diisocyanate (PPDI), m- tetramethyl xylylen diisocyanate (TMXDI) etc. and its dimer.Preferably HDI, IPDI, MDI Or TDI.

Suitable triisocyanate is the trimer or biuret of aliphatic, alicyclic, aromatics or araliphatic diisocyanate, Particularly the preceding paragraph falls the isocyanuric acid ester and biuret of described diisocyanate.

Y in formula (II) or (IV)₁Another possibility for molecule remove X₁Chain group after H- groups, institute Chain group is stated in form by with the dihydric alcohol or trihydroxylic alcohol and/or diamines or triamine that have been described above and having retouched Similar reaction of reacting between the diisocyanate or triisocyanate stated is obtained.This stoichiometric proportion by reacting object Change and realize therefore there are two kinds of possibilities.

On the one hand the X excessive relative to NCO- groups can be passed through₁H- groups obtain the OH- functions with different chain length Polymer.The polyalcohol or polyamines of the chain of the formula (IV) include carbamate groups or urea groups in chain, and can Further to be reacted with other diisocyanate or triisocyanate, so as to form formula (II) polymer.On the other hand can be with By relative to the insufficient amount of X of NCO- groups₁H- groups obtain the polymer of the NCO- functions with different chain length.

The chain length and the degree of cross linking of the formula (II) or (IV) chain polymer depend highly on molar ratio [X₁H]/ [NCO].The ratio is closer to 1, and chain is longer.It will be clear to someone skilled in the art that long chain or too high degree of cross linking meeting Cause no longer available polymer.Increase for chain, particularly preferred dihydric alcohol or diamines and diisocyanate.

The isocyanate-terminated compound of formula (II) preferably can be by with X₁The prepolymer of H- groups and one kind or many The reaction for planting polyisocyanates is obtained, described to carry X₁The prepolymer of H- groups be selected from PPG, polybutadiene polyol, PEPA, polycarbonate polyol, the polyethers and its mixture of NH- end-blockings, the polyisocyanates is specifically for two isocyanides Acid esters and/or triisocyanate.Preferably, with aromatics or aliphatic vulcabond or triisocyanate (such as IPDI, HDI, MDI, TDI etc.) carry out OH-, SH- or NH- end-blocking polymer (particularly those described above, for example polypropylene glycol, Jeffamine, Hydroxy-end capped polybutadiene etc.) it is isocyanate-terminated.

In an alternate embodiment, in order to prepare the isocyanate-terminated compound of formula (II), except as above Described carries X₁Outside the prepolymer and polyisocyanates of H- groups, also mix polyhydric phenols to be reacted.Exemplified by polyhydric phenols Such as bis-phenol, triphenol and/or four phenol, wherein it can be unsubstituted or substituted polyhydric phenols.Formula (II) is obtained in this case Comprising at least one aromatic structure unit in isocyanate-terminated compound, the compound, the aromatic structure unit leads to Carbamate groups are crossed to combine in polymer chain.The compound is described in detail in WO 2005/007720, the text Offer and be hereby incorporated herein by, especially with regard to the details prepared with workable component.Suitable polyhydric phenols and suitable Preparation approach description at page 9 and 10 or 13 and 14 of the document.

In order to prepare the liquid rubber for including the impact modifier that epoxide group is blocked, seal one or more isocyanates The prepolymer at end reacts with epoxy resin, and the epoxy resin includes the epoxide with primary hydroxyl or secondary hydroxyl.Formula (III) hydroxy-epoxy compound has 1,2 or 3 epoxide groups.The hydroxyl of the hydroxy-epoxy compound (III) can be with For primary hydroxyl or secondary hydroxyl.The hydroxy-epoxy compound of formula (III) is preferably monohydroxy-epoxide.

For the epoxy resin with isocyanate-terminated prepolymer reaction can for epoxy resin or two or more The mixture of epoxy resin.Epoxy resin is specifically for liquid epoxies.Epoxy resin is included or by constituting as follows：Hydroxyl The hydroxy-epoxy compound of material, particularly formula (III).Epoxy resin or liquid epoxies can be the ring of commercially available acquisition Oxygen tree fat prod.

Epoxy resin is for example by epoxide (such as epichlorohydrin) and polyfunctional alcohol (i.e. dihydric alcohol, trihydroxylic alcohol or polynary Alcohol) reaction obtain.According to reaction process polyfunctional alcohol from the reaction of epoxide (such as epichlorohydrin) with different dense Degree forms the corresponding hydroxy-epoxy compound as accessory substance.Hydroxyl-the ring can be separated by common lock out operation Oxygen compound.But according to the invention, it is possible to use obtained in the glycidol glycosylation reaction of polyalcohol by complete and portion The product mixtures that the polyalcohol for dividing reaction to form glycidol ether is constituted.These hydroxyl epoxides in epoxy resin Example is the trimethylolpropane diglycidyl ether being included in as mixture in trihydroxymethylpropanyltri diglycidyl ether, is made The glycerin diglycidyl ether in T 55 is included in for mixture, pentaerythrite four is included in as mixture Pentaerythrite triglycidyl ether in glycidol ether.In a preferred embodiment, hydroxyl epoxides is three Hydroxymethyl-propane diglycidyl ether, it is in conventional obtained trihydroxymethylpropanyltri diglycidyl ether with relatively high share In the presence of.But other similar hydroxyl epoxides, particularly glycidol, 3- glycidoxypropyl benzene first can also be used Alcohol or hydroxymethyl -7-oxa-bicyclo[4.1.0.Preferably include trimethylolpropane diglycidyl ether, butanediol 2-glycidyl The epoxy resin of ether, cyclohexanedimethanodiglycidyl diglycidyl ether or its mixture.

It can also use below for the formula (III) included with primary hydroxyl or secondary hydroxyl described by epoxy resin (A) The liquid epoxies of other formulas (VII) of epoxide.

Particularly preferably it is based on the epoxy resin of the diglycidyl ether of bisphenol-A (BADGE), Bisphenol F or bisphenol-A/F. These epoxy resin commercially available can be obtained on a large scale.It can by bisphenol-A, Bisphenol F or bisphenol-A and the mixture of Bisphenol F ( It is referred to as bisphenol-A/F) obtained with the reaction of epichlorohydrin.HMW or the production of low molecule quantitative response can be prepared according to reaction process Thing.

Particularly preferable as formula (III) hydroxy-epoxy compound be formula (VI) beta-hydroxy ether

Wherein R is H or methyl independently of one another, and it is included in by bisphenol-A (R=CH with about 15%₃) and epichlorohydrin be made Commercial liquid epoxy resin in, and in the reaction of bisphenol-f (R=H) or the mixture and epichlorohydrin of bisphenol-A and bisphenol-f The corresponding beta-hydroxy ether of middle formation.Except bisphenol-A-diglycidyl ether dimer and with Bisphenol F or bisphenol-A and Bisphenol F Mixture the corresponding dimer according to formula (VI) outside, can also use BADGE- bisphenol-A adductions chain product or with The corresponding product of Bisphenol F, it is for example comprising 3 or 4 bis-phenol units.Work as diglycidyl ether, particularly bisphenol-A (BADGE) or When the diglycidyl ether of bisphenol-f reacts at elevated temperatures with bis-phenol, this growth is especially carried out.Favourable, it is this double The diglycidyl ether that phenol increases is used together with the diglycidyl ether not increased.

Correspondingly, the liquid epoxies of formula (A-I) is preferably used as epoxy resin

Wherein substituent R " ' and R " " H or CH is represented independently of one another₃, and index r has 0.01 to 1, preferably 0.05 To 1 value.Preferably, r represents less than 1, especially less than 0.3, preferably smaller than 0.2 value.In the definition of group, statement " independently of one another " it is here and hereinafter meant that under each case that in formula the group that repeatedly occurs but indicate in the same manner can be with Each there are different implications.

The liquid epoxies of the formula (A-I) is commercially available prod, for exampleGY250、 PY 304、GY 282 (Huntsman or Hexion) or331、330 or332 (Dow) or828(Hexion)。

In another preferred embodiment, it can use to obtain by the reaction of single phenol and epoxy resin and (for example lead to The reaction for crossing p- methoxyl group phenol and D.E.R.332 is obtained) epoxy resin.In addition it can also use by (poly-) epoxides There is hydroxyl ether group not made from reaction with insufficient amount of monovalence nucleopilic reagent (such as carboxylic acid, phenol, triol or secondary amine) Same epoxides.In another embodiment, it can also use what is produced in the preparation that high-purity distills epoxy resin Distillation leftover.This distillation leftover is (for exampleM850 the hydroxyl epoxy compound of significantly higher concentration) is included Thing is used as standard epoxy.

The free primary hydroxyl functional group of the hydroxy-epoxy compound of formula (III) or secondary hydroxyl functional group can be with prepolymers Terminal isocyanate groups effecting reaction, without for this use out-of-proportion excess epoxy compound component.

In order that the isocyanate-terminated prepolymer reaction of formula (II), can use respective amount comprising formula (III) The epoxy resin of hydroxyl epoxides (preferably monohydroxy epoxides).Can use isocyanate groups and hydroxyl etc. rub Molar ratio [OH]/[NCO] of your stoichiometric proportion, i.e., 1, but the ratio can also be deviateed.Suitably, ratio [OH]/ [NCO] is such as 0.6 to 3.0, preferably 0.7 to 1.5, particularly 0.8 to 1.2.

What is obtained has the advantageously flexible feature of liquid rubber of the polymer of epoxide group end-blocking and also has Sharp ground can be dissolved or dispersed in epoxy resin.The liquid rubber can be when needed and according to the other rings of gained viscosity Oxygen resins dilute.The diglycidyl ether of bisphenol-A, bisphenol-f and bisphenol-A/F is preferably for this, and it is hereafter further The reactive diluent with epoxide group of description, particularly hexanediol diglycidyl ether, polypropylene glycol diglycidyl Ether and trihydroxymethylpropanyltri diglycidyl ether.

According to the present invention, in the synthesis for the polyether polyols that epoxy resin is blocked using it is at least one selected from acid anhydrides, The compound of ketone and aldehyde is used as glycol capturing agent.In the case of using acid anhydrides, the capture of the glycol included in epoxy resin is anti- Should the formation based on the thermodynamically particularly advantageous cyclic ester functional group between acid anhydrides and glycol.With the capture reaction Similar, the glycol included in epoxy resin can also be by being combined with ketone and aldehyde reaction in the form of ketal or acetal.No The liquid rubber for preparing epoxide group end-blocking using glycol capturing agent can cause the notable gel and inhomogeneities of polymer.

The reaction of isocyanate-terminated prepolymer Yu the epoxy resin comprising hydroxy-epoxy compound is in glycol capturing agent In the presence of carry out.Therefore, isocyanate-terminated prepolymer, epoxy resin and glycol capturing agent can before reactions each other Mixing, so as to form reactant mixture, wherein addition sequence is arbitrary.For example can be first into hydroxy-epoxy compound Isocyanate-terminated prepolymer is added, glycol capturing agent is then added, is then mixed by stirring.

In an alternate embodiment, the presence of glycol capturing agent can be achieved in that：Make to include formula (III) first Epoxy resin and the glycol capturing agent of hydroxy-epoxy compound react, then make obtained reaction product and formula (II) Isocyanate-terminated prepolymer mixing and reaction.

Acid anhydrides is preferably used as glycol capturing agent.Acid anhydrides is organic acid anhydride, i.e. carboxylic acid anhydrides.Acid anhydrides or difference can be used The mixture of acid anhydrides.A wide range of acid anhydrides is suitable as containing glycol in epoxy resin or epoxy resin composition in principle The capturing agent of matter.The acid anhydrides of aromatics, cyclic aliphatic, aliphatic series or difunctionality can be used.

Mixed acid anhydride can also be used, but is generally preferably derived from the acid anhydrides of carboxylic acid.Particularly preferably cyclic acid anhydride and Its derivative.The cyclic acid anhydride generally originates from dicarboxylic acids.Derivative is understood to that substitution (for example uses C₁-C₁₈- alkyl, C₁- C₁₈- alkenyl, aryl, fusion alicyclic ring or aromatic ring substitution) acid anhydrides, and/or aromatic moiety or all hydrogenation acid anhydrides.Properly Acid anhydrides example be alkanoic acid anhydride, such as C₂-C₁₈- alkanoic acid anhydride and its derivative, such as acetic anhydride, propionic andydride, butyric anhydride, valeric acid Acid anhydride and stearic anhydride, such as docosandioic acid acid anhydride, C₄-C₈- docosandioic acid acid anhydride and its derivative, such as succinic anhydride, methyl succinic acid anhydrides, (2- dodecylene -1- bases) succinic anhydride, phenylsuccinic acid acid anhydride, glutaric anhydride, methylglutaric acid acid anhydride, 3,3- dimethylated pentanedioic acids Acid anhydride and itaconic anhydride, such as enedioic acid acid anhydride, C₄-C₈- enedioic acid acid anhydride and its derivative, such as maleic anhydride, 2,3- dimethyl Malaysia Acid anhydrides, citraconic anhydride, alicyclic dicarboxylic acid's acid anhydride and its derivative, such as cyclohexane dicarboxylic acid acid anhydride, ENB -2,3- dicarboxylic acids Acid anhydride, methyinorbornene -2,3- dicarboxylic anhydride, camphoric anhydride, aromatic anhydride and its derivative, such as benzoyl oxide, adjacent benzene two Formic anhydride and its derivative, such as methyl nadic anhydride (MPA), methyl tetrahydrophthalic anhydride (MTHPA), tetrahydrochysene are adjacent Phthalate anhydride, tetraphenyl phthalic anhydride, methylhexahydrophthalic anhydride (MHHPA) and hexahydrophthalic anhydride, High phthalic anhydride, 1,2- naphthalic anhydrides and its derivative, such as 3,4- dihydro -1,2- naphthalic anhydrides, difunctional acid Acid anhydride, such as pyromellitic acid dianhydride, benzophenonetetracarboxylic dianhydride and biphenyltetracaboxylic dianhydride and anhydride diethylene glycol.It is preferred that acid anhydrides For succinic anhydride, phthalic anhydride and its derivative, particularly methyl nadic anhydride or 4- methyl nadic anhydrides. Acid anhydrides preferably comprises butanedioic acid anhydro ring or maleic acid anhydro ring as construction unit.

The ketone and the example of aldehyde that can be used according to the present invention as glycol capturing agent are formaldehyde, acetone, cyclopentanone or benzene Formaldehyde, it can combine glycol and form ring-type DOX simultaneously.

In the reactant mixture of the isocyanate-terminated prepolymer comprising formula (II) and epoxy resin, glycol capturing agent Amount can change and depending on species, its ratio and the glycol capturing agent of used specific reaction object in a wide range of Species.For example using at least 0.1 weight %, preferably at least 0.25 weight % and particularly preferably at least 0.4 weight %, and not More than 5.0 weight %, preferably no greater than 3.0 weight % and more preferably no more than 2.50 or 2.75 weight % glycol capturing agent, Preferred anhydrides, with the gauge of used epoxy resin.Particularly preferably using 0.25 to 3.00 weight %, preferably 0.50 to 1.50 weight % glycol capturing agent, preferred anhydrides, with the gauge of used epoxy resin.In the case where crossing low amounts, no The degree for being avoided that gel or avoiding is too low.In the case where crossing a large amount glycol capturing agent, after some time due to reaction The cross-linking reaction formation skinning for falling (i.e. too high isocyanate content) and passing through isocyanates and air moisture.

The epoxides of OH- functions by combining in isocyanate-terminated prepolymer and epoxy resin is captured with glycol The preparation method of the reaction of agent, it is to avoid or minimize the undesirable cross-linking for causing gel.Gel is caused in adhesive Prepolymer it is unusable because be no longer able to ensure processing.

As described above, can so control the OH- official in isocyanate-terminated prepolymer and epoxy resin in the reaction The stoichiometric proportion of the epoxides of energy, so as to obtain completely enclosed polymer.What it is also according to the present invention is partially enclosed Polymer, a portion isocyanate groups keep unreacted so as to for the reaction in following reaction step.Such as following formula (I) compound represent can by according to the present invention reaction obtain completely enclosed polymer, wherein substituent and Index with identical mode in formula (II) and (III) to define.Only partially enclosed polymer corresponds to the compound of formula (I), But wherein simultaneously not all isocyanate groups are closed by hydroxy-epoxy compound.

The method according to the invention can obtain the liquid comprising closing or partially enclosed isocyanate-terminated prepolymer Rubber, it may be used as the impact modifier of the epoxide group end-blocking in one-component or bicomponent epoxy resin composition to rise The impact flexibility of high cured epoxy matrix material.Preferably bicomponent epoxy resin composition.Two-component or one-component ring Epoxy resin composition can be liquid, pasty state or solid and/or cold curing or heat cure.

Composition epoxy resin is preferably one-component or bicomponent epoxy resin adhesive, particularly construction adhesive or resistance to Collide adhesive, for example for OEM- products, EP/PU- mixtures, epoxy-resin systems structural foam (such as Sika) or repairing application.

The liquid rubber according to the present invention is comprised at least according to the one-component or bicomponent epoxy resin composition of the present invention. In addition, including at least one curing agent for epoxy resin according to the epoxide composition of the present invention, the curing agent exists It is present in the case of one-component composition in same component (such as liquid rubber), or in the situation of two-component composition Under be present in the second component.

According to for epoxy resin used in preparing liquid rubber, in addition to the liquid rubber according to the present invention, Other epoxy resin need not be added in one-component or bicomponent epoxy resin composition.But optionally and preferably, can also Include extra epoxy resin (A).Extra epoxy resin (A) can be liquid epoxies or solid epoxy.It is adapted to What it is as epoxy resin (A) is above as described by the epoxy resin for being reacted with isocyanate-terminated prepolymer All epoxy resin.Be described below the other suitable components and its share of composition epoxy resin, the component and Its share is equally applicable to preferred epobond epoxyn.

It is suitable as the diglycidyl ether specifically for formula (VII) of liquid epoxies or solid epoxy (A)

Wherein R⁴Represent divalent aliphatic or monokaryon aromatics or two core aromatic groups.

Be suitable as formula (VII) diglycidyl ether particularly

- difunctionality saturation or unsaturation, branched or non-branching, ring-type or open chain C₂-C₃₀The diglycidyl ether of -ol, example Such as glycol glycidyl ethers, butanediol glycidol ether, hexylene glycol glycidol ether, ethohexadiol glycidol ether, hexamethylene Dimethanol diglycidyl ether, neopentylglycol diglycidyl ether；

- difunctionality low molecule amount is to the diglycidyl ether of the PPG of HMW, such as polyethylene glycol-two Glycidol ether, polypropylene glycol-diglycidyl ether；

The diglycidyl ether of the bis-phenol of-difunctionality and optional triphenol, wherein pure phenol is hereafter not only interpreted as, and The phenol of substitution also is understood as in the case of appropriate.The species of substituent can be very various.Especially, hereinafter it is interpreted as direct In the substituent being bonded with the aromatic kernel of phenols OH-group group.In addition, phenol is not considered only as monokaryon aromatics, also managed Solve as multinuclear or fused aromatic compound or heteroaromatic compound, it has the phenols directly in aromatics or heteroaromatic compound OH-group group.For example be suitable as bis-phenol and optional triphenol be 1,4- dihydroxy benzenes, 1,3- dihydroxy benzenes, 1,2- dihydroxy benzenes, 1,3- orcins, 3,5- dihydroxy-benzoic acids salt, 2,2- double (4- hydroxy phenyls) propane (=bisphenol-A), double (4- hydroxyls Phenyl) methane (=bisphenol-f), double (4- hydroxy phenyls) sulfones (=bis-phenol-S), naphthoresorcine, dihydroxy naphthlene, dihydroxy-anthracene Double (p- hydroxy phenyl) phthalides of quinone, dihydroxy-biphenyl, 3,3-, double (4- hydroxy phenyls) hexahydro -4,7- endo-methylene group indenes of 5,5- Full, phenolphthalein, fluorescein, 4,4'- [double-(hydroxy phenyl) -1,3- phenylene pair-(1- methyl-ethylenes)] (=bis-phenol-M), 4, 4'- [double-(hydroxy phenyl) -1,4- phenylene pair-(1- methyl-ethylenes)] (=bis-phenol-P), 2,2'- diallyl-bisphenols - A, pass through bis-phenol made from the reaction of phenol or cresols and diisopropylidene benzene and xylenol, phloroglucin, gallate, OH- Degree of functionality is 2.0 to 3.5 novolaks or all isomers of cresol novolak and above-claimed cpd.

Particularly preferable as formula (VII) diglycidyl ether be formula (A-I) liquid epoxies and formula (A-II) Solid epoxy.

', R ", R " ' and R " here, substituent R " represents H or CH independently of one another₃.In addition index r represents 0 to 1 value.r It is preferred that representing less than 0.2 value.In addition, index s is represented>1, particularly>The value of 1.5, particularly 2 to 12.

The compound of formulas (A-II) of the index s between 1 and 1.5 is generally referred to by those skilled in the art as semi-solid asphalt mixtures modified by epoxy resin Fat.The semi-solid epoxy resin is equally considered to be hard resin for the present invention.But it is preferred that solid in the narrow sense Epoxy resin, i.e. index s has>1.5 value.

This solid epoxy can for example be obtained from Dow or Huntsman or Hexion are commercially available.Formula (the A- of commercially available acquisition I liquid epoxies) has been described above.

Preferably, the diglycidyl ether of formula (VII) is liquid epoxies, particularly bisphenol-A (BADGE), bisphenol-f And bisphenol-A/F diglycidyl ether.

In one embodiment, it is suitable as the particularly such as art technology of the curing agent of composition epoxy resin Personnel know as the polyamines of curing agent, polythiol, Polyamide amine, amino-functional polyamines/polyepoxide-adduct. In this embodiment, composition is the two-component ring being made up of two kinds of components, i.e. the first component (K1) and the second component (K2) Epoxy resin composition.First component (K1) comprises at least the liquid rubber and optionally extra liquid epoxies according to the present invention And/or solid epoxy (A).Second component (K2) includes at least one curing agent for epoxy resin.First component (K1) each it is stored in the second component (K2) in autonomous container.Just be mixed with each other two kinds of components and reactivity when use Composition is reacted with each other, therefore causes the crosslinking of composition.This bicomponent epoxy resin composition is generally at 0 DEG C to 100 DEG C Between in a low temperature of, particularly it is curable at room temperature.In the embodiment described in which, solidification passes through curing agent and composition Present in have epoxide group compound between addition reaction and carry out.Therefore it is particularly advantageous in the embodiment described in which , amount of the curing agent in whole composition is so set so that epoxide reaction group relative to epoxide group with Stoichiometric proportion is present.

In an alternate embodiment, especially for one-component composition, the curing agent for epoxy resin is Pass through the curing agent of elevated temperature-activated.In this embodiment, composition is the composition epoxy resin of heat cure." rise High temperature " is generally understood as more than 100 DEG C herein, particularly the temperature between 110 DEG C and 200 DEG C.By rising High temperature and the curing agent for epoxy resin that activates is preferably selected from dicyandiamide, guanamines, guanidine, aminoguanidine and its derivative Curing agent.Furthermore it is possible that the curing agent with acceleration, such as chloro- 4- aminomethyl phenyls urea of substituted urea, such as 3- (chlortoluron), or phenyl dimethyl urea, particularly rubigan-N, N- dimethyl ureas (telvar), 3- phenyl -1,1- dimethyl Urea (fenuron) or 3,4- dichlorophenyls-N, N- dimethyl urea (diuron) and the urea of aliphatic series substitution.Imidazoles can also be used Class compound, such as 2 isopropyl imidazole or 2- hydroxy-ns-(2- (2- (2- hydroxy phenyls) -4,5- glyoxalidine -1- bases) second Base) benzamide and amine complex.

Preferably, it is selected from following curing agent by hot activable curing agent：Dicyandiamide, guanamines, guanidine, aminoguanidine and Its derivative；The chloro- 4- aminomethyl phenyls urea (chlortoluron) of substituted urea, particularly 3-, or phenyl dimethyl urea, particularly to chlorobenzene Base-N, N- dimethyl urea (telvar), 3- phenyl -1,1- dimethyl urea (fenuron), 3,4- dichlorophenyl-N, N- dimethyl ureas (diuron) or the urea of aliphatic series substitution, and imidazoles and amine complex.It is dicyandiamide particularly preferable as curing agent.

Advantageously, total share for the curing agent activated by elevated temperature of epoxy resin is 0.5 to 12 weight Measure %, preferably 1 to 8 weight %, in terms of the weight of whole composition.

Preferably, composition is described impact-resistant modified also comprising at least one extra optional impact modifier (SM) Agent (SM) is different from the impact modifier that the epoxides in the above-mentioned liquid rubber according to the present invention is blocked.Described extra resists Impact modifier (SM) can be solid or liquid.

In one embodiment, the extra impact modifier (SM) be liquid rubber (SM1), its be carboxy blocking or Acrylonitrile/butadiene-copolymer of epoxides end-blocking or derivatives thereof.This liquid rubber is for example with Emerald Performance Materials LLC title(it is before) CTBN and CTBNX and ETBN it is commercially available Obtain.Be suitable as derivative particularly with epoxide group elastomer-modified prepolymer, for example with The product line of company (Schill+Seilacher Gruppe, Germany)Preferred product line36.. Or with product lineThose of (Evonik Hanse GmbH, Germany) commercial distribution.In another embodiment In, impact modifier (SM) is polyacrylate liquid rubber (SM1), and the polyacrylate liquid rubber (SM1) can be with Liquid epoxies is thoroughly mixed and is just separated into droplet when epoxy matrix material solidifies.This polyacrylate liquid rubber Glue is for example obtained with title 20208-XPA from Rohm und Haas.

It will be clear to someone skilled in the art that the mixture of liquid rubber, particularly carboxy blocking can certainly be used Or the polyurethane prepolymer that is blocked with epoxides of acrylonitrile/butadiene-copolymer or derivatives thereof of epoxides end-blocking Mixture.

In another embodiment, extra impact modifier (SM) can be solid impact modifier, and it is organic Ion exchange layered minerals material.The layered minerals material of ion exchange can be cation exchange or the stratiform of anion exchange Mineral matter.It is also possible that composition includes the layered minerals material of cation exchange and the layered minerals of anion exchange simultaneously Material.

The layered minerals material of cation exchange is obtained by layered minerals material herein, and a part of cation of wherein at least is organic Cation exchange.The example of the layered minerals material of this cation exchange particularly institute in US 5707439 or US 6197849 Those stated.The method that the layered minerals material for preparing the cation exchange is also described in the document.Preferably as Layered minerals material is phyllosilicate.It is particularly preferred that layered minerals material is phyllosilicate, such as on the columns of US6197849 the 2nd 38th row is to those described in the row of the 3rd column the 5th, particularly bentonite.It is proved to be particularly suitable to such as kaolinite or illiteracy De- soil or hectorite or illitic layered minerals material.

At least a portion cation of layered minerals material is substituted by organic cation.The example of this cation is n-octyl Ammonium, trimethyldodecane base ammonium, dimethyl dodecyl base ammonium or double (hydroxyethyl) octadecyl ammoniums can be by natural fats The similar derivatives of the amine obtained with oil；Or guanidine cation or acid amides cation；Or pyrrolidines, piperidines, piperazine, morpholine, The cation of the derivative of the N- substitutions of thiomorpholine；Or 1,4- diazabicyclos [2.2.2] octane (DABCO) and 1- azepines pair The cation of ring [2.2.2] octane；Or pyridine, pyrroles, imidazoles, oxazoles, pyrimidine, quinoline, isoquinolin, pyrazine, indoles, benzo miaow Azoles, benzoxazole, the cation of the derivative of the N- substitutions of thiazole azophenlyene and the pyridines of 2,2'- bis-.Also suitably from cyclic amide Cation, the row of the 3rd column the 6th is to the row those disclosed of the 4th column the 67th particularly such as in US 6197849.

It is preferred that cation exchange layered minerals material with title organic clay or nanoclay by those skilled in the art , it is known that and for example with group nameOr(Südchemie)、(Southern Clay Products) or(Nanocor Inc.) or(Rockwood) it is commercially available to obtain.

The layered minerals material of anion exchange is obtained by layered minerals material herein, and a part of anion of wherein at least is organic Anion exchange.The example of the layered minerals material of anion exchange is at least a portion carbonate of hydrotalcite, wherein intermediate layer Anion is exchanged by organic anion.

In another embodiment, extra impact modifier (SM) can be solid impact modifier, and it is block Copolymer (SM2).Block copolymer (SM2) by methacrylate and at least another monomer with olefinic double bond the moon from Son polymerization or controlled radical polymerization and obtain.As the monomer with olefinic double bond, particularly preferably double bond directly with Hetero atom or those being conjugated with least another double bond.It is particularly suitable to be selected from styrene, butadiene, acrylonitrile and acetic acid The monomer of vinyl acetate.Preferably for example can be with title1020 acrylate obtained from GE Plastics- Styrene And Chloroalkyl Acrylates (ASA)-copolymer.Particularly preferred block copolymer (SM2) be methyl methacrylate, styrene and The block copolymer of butadiene.This block copolymer is for example obtained as triblock copolymer with group name SBM from Arkema.

In another embodiment, extra impact modifier (SM) is core shell polymer (SM3).Core shell polymer It is made up of elastic nuclear polymer and rigid shell polymeric.Specially suitable core shell polymer is by by rigid thermoplastic polymer Elastic acrylate polymer or core (Core) composition of butadiene polymer that shell (shell) is surrounded.The core/shell structure leads to Cross the separation of block copolymer and automatically form, or the polymerisation run by emulsion polymerization or suspension polymerisation form with it is subsequent It is grafted and is formed.It is preferred that core shell polymer be so-called MBS- polymer, it is with Arkema trade (brand) nameDow (being before Rohm und Haas) trade (brand) nameOr Zeon trade (brand) nameIt is commercially available to obtain.

Particularly preferably as the core shell polymer beads existed through dry polymer latex.The example is Wacker's has polysiloxanes core and acrylate shellNEP systems prepared by M23A, Eliokem The rubber grain of the crosslinking with radiation of row, or LanxessOr DowEXL.Core shell is gathered Other suitable examples of compound are with German Evonik Hanse GmbH titleThere is provided.It is also desirable to Nanometer scale silicate in epoxide substrate, for example, sold with German Evonik Hanse GmbH trade (brand) name Nonopox Nanometer scale silicate.

In another embodiment, extra impact modifier (SM) is carboxylation solid nitrite rubber and excess epoxy resin Reaction product (SM4).

It has been found that being advantageously present one or more extra impact modifiers (SM) in the composition.It was found that special Not advantageously, other impact modifiers (SM) are the impact modifier with epoxide group of formula (VIII).

In this R⁷For carboxy blocking butadiene/acrylonitrile-copolymer (CTBN) remove terminal carboxyl group after divalence Group.Group R⁴With with formula (VII) identical mode is defined and described above.Especially, R⁷Represent by removing in form With titleCTBN is obtained by butadiene/acrylonitrile-copolymer CTBN of the Noveon carboxy blockings sold carboxyl The group obtained.R⁷The preferably divalent group of formula (VIII').

R⁰Represent that there is 1 to 6 carbon atom, the linear or branched alkylidene of particularly 5 carbon atoms, the Asia herein Alkyl is optionally replaced by unsaturated group.In an embodiment for needing specifically mentioned, substituent R⁰For formula (VlII-a) Group.

In addition, index q' is represented between 40 and 100, the value between 50 and 90 is particularly.Mark b and c represents to be derived from The construction unit of butadiene, a represents the construction unit from acrylonitrile.Index x, m' and p' represent respectively description scheme unit a, The value of the mutual ratios of b and c.Index x represents 0.05 to 0.3 value, exponent m ' represent 0.5-0.8 value, index p represents 0.1- 0.2 value, on condition that x, m' and p summation are equal to 1.

It will be appreciated by those skilled in the art that the structure of display is managed in the way of simplifying diagram in formula (VIII') Solution.Therefore, unit a, b and c is each arranged each other in the way of random, alternating or block.Therefore especially, formula (VIII') is no One is set to triblock copolymer.

By being particularly formula (IX), (wherein substituent is with identical with formula (VIII) for the preparation of the impact modifier of formula (VIII) Mode define) carboxy blocking butadiene/acrylonitrile-copolymer (CTBN) and above-mentioned formula (VII) diglycidyl ether With the excessive amount of stoichiometrically diglycidyl ether, (i.e. the ratio of glycidyl ether group and COOH- groups is more than or equal to 2) react and carry out.

Above-mentioned one kind or many of the impact modifier blocked different from the epoxides in the liquid rubber according to the present invention The share for planting extra impact modifier (SM) is such as 0 to 45 weight %, preferably 1 to 45 weight %, particularly 3 to 35 weights % is measured, in terms of the weight of whole composition.

The composition can also include other compositions certainly.Other compositions particularly filler (F), reactivity dilution Agent (G), such as reactive diluent with epoxide group, catalyst, particularly stabilizer, heat stabilizer and/or light are stable Live on agent, thixotropic agent, plasticizer, solvent, mineral filler or organic filler, foaming agent, colouring agent and pigment, anticorrosive, surface Property agent, defoamer and tackifier.For these additives, can with common amount using it is known in the prior art it is all that A bit.

Filler (F) is for example preferably mica, talcum, kaolin, wollastonite, feldspar, syenite, chlorite, bentonite, illiteracy De- soil, calcium carbonate (precipitate or grind), dolomite, quartz, silica (pyrolysis is precipitated), cristobalite, calcium oxide, hydrogen-oxygen Change aluminium, magnesia, ceramic hollow ball, glass hollow ball, organic hollow ball, glass marble, coloring pigment.Filler (F) means organic It is coating and uncoated to be commercially available and form well known by persons skilled in the art.

Advantageously, total share of all fillers (F) is 3 to 50 weight %, preferably 5 to 35 weight %, particularly 5 to 25 weights % is measured, in terms of the weight of whole composition.

Reactive diluent (G) specifically for：

- simple function saturation or unsaturation, branched or non-branching, the C of ring-type or open chain₄-C₃₀The glycidol ether of -ol, it is special Xuan Zi not butanol glycidol ether, hexanol glycidol ether, 2-Ethylhexyl Alcohol glycidol ether, allyl glycidyl ether, four Tetrahydrofurfuryl glycidol ether and furfuryl glycidyl ether, trimethoxysilyl glycidol ether.

- difunctionality saturation or unsaturation, branched or non-branching, the C of ring-type or open chain₂-C₃₀The glycidol ether of -ol, it is special Xuan Zi not glycol glycidyl ethers, butanediol glycidol ether, hexylene glycol glycidol ether, ethohexadiol glycidol ether, ring Hexane dimethanol diglycidyl ether and neopentylglycol diglycidyl ether.

- trifunctional or polyfunctional saturation or unsaturation, branched or non-branching, alcohol (such as epoxidation of ring-type or open chain Castor oil, epoxidation trimethylolpropane, epoxidation pentaerythrite) glycidol ether, or aliphatic polyol (such as sorb Alcohol, glycerine or trimethylolpropane) polyglycidyl ether.

The glycidol ether of-oxybenzene compound and aniline compound, contracts in particular selected from phenyl glycidyl ether, tolyl Water glycerin ether, p- tbutyl-phenyl glycidol ether, nonyl phenol glycidol ether, the positive 15 alkenyl glycidol ethers of 3- ( From cashew nut shell oil), N, the triglycidyl group of N- diglycidylanilines and para-aminophenol.

- epoxidation amine, such as N, N- diglycidyl cyclohexylamine.

- epoxidised monocarboxylic acid or dicarboxylic acids, in particular selected from glycidyl neodecanoate, methyl propenoic acid glycidyl Ester, glycidyl benzoate, o-phthalic acid diglycidyl ester, tetrahydrochysene and hexahydrophthalic acid 2-glycidyl ester and The 2-glycidyl ester and terephthaldehyde's acid glycidyl ester and trimellitic acid ethylene oxidic ester of dimer (fatty acid) yl.

- epoxidised two function or trifunctional, the PPG of low molecule amount to HMW, particularly poly- second two Alcohol diglycidyl ether or polypropylene glycol-diglycidyl ether.

Particularly preferably hexanediol diglycidyl ether, cresyl glycidyl ether, p- tert-butyl-phenyl glycidol Ether, polypropylene glycol diglycidyl ether and polyethyleneglycol diglycidylether.

Advantageously, total share of reactive diluent (G) is 0.1 to 20 weight %, preferably 1 to 8 weight %, with whole group The weight meter of compound.

Be suitable as plasticizer for for example can be withOr the phenol that Dellatol BBS are obtained from Bayer Alkyl sulfonic ester or benzene sulfonic acid-N- butyramides.Be suitable as stabilizer is for example optionally substituted phenol, such as butylhydroxy Toluene (BHT) orT (Elikem), bulky amine or N- oxo-compounds such as TEMPO (Evonik).

In a special embodiment, composition also especially includes at least one physics with 0.1 to 3 weight % amount Or CBA, in terms of the weight of composition.It is preferred that foaming agent be CBA, the CBA heating When, especially discharge gas when being heated to 100 to 200 DEG C of temperature.It can be exothermic blowing agent, such as nitric heterocyclic compound, Hydrazine derivate, semicarbazides or tetrazolium.The azodicarbonamide and oxygen-bis- (benzenesulfonyls preferably released energy when decomposing Hydrazides).Also suitably from Endothermic blowing agents, such as sodium bicarbonate/citric acid mixtures.This CBA for example with The title of Chemtura companiesObtain.Equally suitable is with the trade (brand) name of Akzo Nobel companiesThe physical blowing agent of sale.WithIt is particularly preferred.

For with according to the present invention comprising epoxide group block impact modifier liquid rubber one-component and Bicomponent epoxy resin adhesive, also exemplarily lists preferred composition and its share.Percent data is by weight.

Single-component adhesive：

A) 0-60% base epoxy resin (liquid resin, hard resin, epoxidised novolaks etc.)

B) 20-80%, preferably 30-60% mixed with liquid resin (BADGE etc.) according to the present invention it is epoxy-capped PU- polymer

C) the PU- polymer of 0-40%, preferably 10-25% closing

D) 0-30%, preferably 5-20% CTBN- derivatives (such as the Hycar- adducts with BADGE)

E) 0-15%, preferably 2.5-7.5% reactive diluent (such as hexanediol diglycidyl ether)

F) 0-25% other non-reacted toughener rubber grains (SM2), nanoscale core shell-paste (SM3) or HAT- Paste (adduct MDI and dibutyl amine, referring to EP 1152019)

G) 2-10%, preferably 3-4.5% curing agent and catalyst

H) 10-40%, preferably 15-25% organic filler or mineral filler

I) additive and auxiliary agent (such as levelling agent, pigment, tackifier)

Two-component adhesive：

A- components：

A) the 5-80%, preferably 30-60% mixed with liquid resin (BADGE etc.) mixing closing/partially enclosed poly- Compound

B) 0-50% liquid resin (BADGE etc.)

C) 0-20% hard resin

D) 0-10% reactive diluent (such as hexanediol diglycidyl ether)

E) 0-25% CTBN- derivatives (such as with BADGE)

F) 0-25% other non-reacted toughener rubber grains (SM2), nanoscale core shell-paste (SM3) or HAT- Paste (adduct MDI and dibutyl amine, EP 1152019)

G) 0-50% organic filler or mineral filler

H) additive and auxiliary agent (such as levelling agent, pigment, tackifier)

B- components：

A) 0-60% aliphatic series, alicyclic polyamine (and/or its epoxy adduct)

B) 0-60% polyoxyalkylene amine

C) 0-60% polyamide/imidazoline (and/or its epoxy adduct)

D) 0-60% amido amine (and/or its epoxy adduct)

E) 0-60% polyoxyalkyl based polyamide (and/or its epoxy adduct)

F) 0-60% Mannich base or phenolic aldehyde amine (and/or its epoxy adduct)

G) 0-10% tertiary amine

H) 0-50% organic filler or mineral filler

I) additive and auxiliary agent (such as levelling agent, pigment, tackifier)

Preferred polyamines for curing agent (B- components) is polyetheramine, such as 4,7,10- trioxa -1,13- tridecanes Diamines, 4,9- dioxa dodecane -1,12- diamines, trioxa -1, the 13- tridecane diamine of adduct such as 4,7,10-, 4,9- bis- Oxa- dodecane -1,12- diamines, and polyoxyalkylene amine is (for exampleD400).Phenolic aldehyde amine is for example3460, pure aliphatic amine, or the aliphatic polyether structure such as Jeffamin RFD270 mixed.

In the case of bicomponent epoxy resin composition, mix the first component (K1) and the second component (K2) it is laggard Row reaction, the reaction causes composition to solidify.(i.e. single-component thermosetting epoxy composite in another embodiment Thing), by the way that composition to be heated to the temperature of the thermal activation more than heat-activatable curing agent so as to be solidified.Solidification temperature is excellent Elect the temperature in the range of 100 DEG C to 220 DEG C, preferably 120 to 200 DEG C as.

The composition is particularly suitable as adhesive and is preferred for bonding at least two base materials.Described adhesive is special It is not suitable for the add-on module of automobile or vehicle or module is installed.In addition, being applied also for according to the composition of the present invention other Application field.Especially it should be noted that in the vehicles (such as ship, lorry, bus or rail vehicle), in day In the manufacture of articles for use (such as washing machine), and for example as the related application of reinforcing construction adhesive in manufacture field. Than adhesives, sealing material or coating can also be realized using according to the composition of the present invention.

Material to be bonded or to be coated is preferably metal and plastics such as ABS, polyamide, polyphenylene oxide, composite example Such as SMC, unsaturated polyester (UP) GFK, epoxides composite or acrylate compound material.Preferably at least a kind of material is The application of metal.Particularly preferred application is the identical or different metal of bonding, particularly in the white body in auto industry. It is preferred that metal be mainly steel, particularly electrogalvanising, galvanizing, the steel of oiling, coat the steel of Beaune zinc, and then phosphatization Steel, and aluminium, the variant form particularly generally occurred within automobile making.

Embodiment

Some embodiments are listed herein below, the embodiment is expanded on further the present invention but should not limited in any way The scope of the present invention.As long as no other explanations, all parts and percentages data are by weight.

Table 1

Prepare embodiment 1：The prepolymer 1 of NCO- end-blockings

700.00g PolyTHF 2000 (OH- value 57.0mg/g KOH), 700.00g are dried at vacuum and 90 DEG C Poly BD R45V (OH- value 43.7mg/g KOH) and 7.00g BHT (being used as stabilizer) 1 hour.Then 280.54g is added IPDI and 0.215g dibutyl tin laurates (DBTL).Reaction 2 hours is carried out at vacuum and 90 DEG C.Measured is free NCO- contents：3.031% (theoretical NCO- contents：3.090%).

Prepare embodiment 2：The prepolymer 2 of NCO- end-blockings

350.00g PolyTHF 2000 (OH- value 55.9mg/g KOH), 350.00g are dried at vacuum and 90 DEG C Poly BD R45V (OH- value 46mg/g KOH) and 3.5g BHT (being used as stabilizer) 1 hour.Then 111.15g IPDI are added With 0.108g DBTL.Reaction 2 hours is carried out at vacuum and 90 DEG C.Measured free NCO- contents：3.237% is (theoretical NCO- contents：3.119%).

Embodiment 1

Dried under 90 DEG C and vacuum828LVEL 2 hours.By 120g in embodiment 1 is prepared it is obtained The prepolymer 1 of NCO- end-blockings is preset in a reservoir.428.565g is added thereto through dry828LVEL.So 1.071g 4- methyl nadic anhydrides (0.25 weight %, with epoxy resin) are added afterwards, then rapid mixing.Mixture Middle addition 0.110g DBTL and reaction 2 hours at vacuum and 110 DEG C.

Embodiment 2

Dried under 90 DEG C and vacuum828LVEL 2 hours.By 120g in embodiment 1 is prepared it is obtained The prepolymer 1 of NCO- end-blockings is preset in a reservoir.428.565g is added thereto through dry828LVEL.So 2.142g 4- methyl nadic anhydrides (0.5 weight %, with epoxy resin) are added afterwards, then rapid mixing.In mixture Add 0.110g DBTL and reacted 2 hours at vacuum and 110 DEG C.

Embodiment 3

Dried under 90 DEG C and vacuum828LVEL 2 hours.120g is made in embodiment 1 is prepared NCO- end-blocking prepolymer 1 it is preset in a reservoir.428.565g is added thereto through dry828LVEL。 Then 3.214g 4- methyl nadic anhydrides (0.75 weight %, with epoxy resin) are added, then rapid mixing.Mixing 0.110g DBTL are added in thing and are reacted 2 hours at vacuum and 110 DEG C.

Embodiment 4

Dried under 90 DEG C and vacuum828LVEL 2 hours.By 120g in embodiment 1 is prepared it is obtained The prepolymer 1 of NCO- end-blockings is preset in a reservoir.428.565g is added thereto through dry828LVEL.So 6.428g 4- methyl nadic anhydrides (1.5 weight %, with epoxy resin) are added afterwards, then rapid mixing.In mixture Add 0.111g DBTL and reacted 2 hours at vacuum and 110 DEG C.

Embodiment 5

Dried under 90 DEG C and vacuum828LVEL 2 hours.By 120g in embodiment 2 is prepared it is obtained The prepolymer 2 of NCO- end-blockings is preset in a reservoir.513.565g is added thereto through dry828LVEL.So 15.407g 4- methyl nadic anhydrides (3.0 weight %, with epoxy resin) are added afterwards, then rapid mixing.Mixture Middle addition 0.130g DBTL and reaction 3 hours at vacuum and 110 DEG C.

Embodiment 6

Dried under 90 DEG C and vacuum828LVEL 2 hours.By 120g in embodiment 2 is prepared it is obtained The prepolymer 2 of NCO- end-blockings is preset in a reservoir.513.565g is added thereto through dry828LVEL.So 26.678g 4- methyl nadic anhydrides (5.0 weight %, with epoxy resin) are added afterwards, then rapid mixing.Mixture Middle addition 0.132g DBTL and reaction 3 hours at vacuum and 110 DEG C.

Comparative example 1

Dried under 90 DEG C and vacuum828LVEL 2 hours.By 120g in embodiment 1 is prepared it is obtained The prepolymer 1 of NCO- end-blockings is preset in a reservoir.428.565g is added thereto through dry828LVEL.It is fast Speed mixing and addition 0.110g DBTL and reaction 2 hours at vacuum and 110 DEG C into mixture.

The result of embodiment 1 to 6 and comparative example 1 is listed in table 2.Can not be without solidifying as can be seen that being added without acid anhydrides Prepare product glue.It will be appreciated also that finding out, adding the viscosity of the reactant mixture of acid anhydrides significantly reduces.Therefore acid anhydrides ensure that The preparation of process safety.Being derived from the range of 0.5 to 1.5% acid anhydrides after certain storage time can liquid processing Toughener.In the case of higher amount acid anhydrides, product passes through the crosslinking of isocyanates and air moisture due to slowly reacting away React and form skinning.Although there is process safety, extended storage stability is limited.

Table 2

Embodiment 7 to 10 and comparative example 2

It is similar to embodiment 1 to 6 and comparative example 1, in MPA presence in embodiment 7 to 10 and comparative example 2 It is lower that isocyanate-terminated prepolymer is closed with epoxide, wherein using331 replace828LVEL is used as epoxide.The result of embodiment 7 to 10 and comparative example 2 is listed in table 3.

Table 3

Embodiment 11 to 16

Make the isocyanate-terminated prepolymers of 150g (by 60 weight % PolyTHF, 40 weight % Poly bd R45V, IPDI (0.75 equivalent) and DBTL are made) mixed with 1 equivalent through dry Epikote 828LVEL.Add thereto Then 8.11mmmol acid anhydrides, mixed material is reacted by adding catalyst at vacuum and 110 DEG C.Select methyl O-phthalic Acid anhydrides (embodiment 11) and phthalic anhydride (embodiment 12) select methylhexahydrophthalic anhydride as aromatic anhydride (embodiment 13), methyinorbornene -2,3- dicarboxylic anhydride (embodiment 14) select dodecenyl succinate as alicyclic acid anhydrides Acid anhydrides (embodiment 15) is used as the succinic acid derivative with aliphatic substituent, and selection pyromellitic dianhydride (embodiment 16) conduct Difunctionality acid anhydrides.The results are shown in Table 4.

The impact modifier with epoxy resin sealing is prepared using all selected acid anhydrides with can ensureing process safety. Do not occur gel under any circumstance during impact modifier is prepared.

The visual assessment of gellation

The gellation of each single material is visually assessed using the fracture tendency of the material sample of each material.Therefore, Wooden scraper is immersed into material and pulled out with hand with moderate speed, until causing the gluey wire drawing to be formed to be broken.Coagulate completely The sample of glue becomes harder and shows the more rapid wire drawing fracture of compared to elasticity, incomplete gel material.

The determination of isocyanate content：

The isocyanic acid represented by using the back titration determination of the di-n-butylamine and 0.1M hydrochloric acid that are excessively used with weight % Ester content.Carried out on the T70 type Mettler-Toledo titration kits determined with automatic potentiometer end points in semi-manual mode It is all to determine.Therefore, 600-800mg samples to be determined are dissolved in 10ml isopropanols and 40ml dimethylbenzene by heat tracing respectively In mixture, the then solution reaction with dibutyl amine in dimethylbenzene.With the excessive di-n-butylamine of 0.1M HCIs and by This calculates isocyanate content.

The determination of viscosity：

By using board-to-board geometry with following parameter on the manufacturer Anton Paar type rheometers of MCR 101 Viscosity measurement is carried out in a rotative pattern：50s^-1Turn, 0.2mm gaps, board-to-board-apart from 25mm.

The exemplary preparation of two-component adhesive based on reactive fluid rubber

Following examples further illustrate reactive fluid rubber as the purposes of impact modifier, but not with any side Formula limits the scope of the present invention.The raw material used in this is given in table 4.

Table 4

In order to prepare A- components, by the reactivity of 163.2g embodiments 9 under 60 DEG C and vacuum in planetary-type mixer Liquid rubber and 109.8g epoxy resin331st, 6.0g tackifierDY91158,0.6g asphalt mixtures modified by epoxy resin Fat blueness paste, 9.0g5GU and 12gR202 stirs into smooth paste.Lead at room temperature Cross and 285g is mixed in planetary-type mixer1922A and 15gK 54 prepares liquid B- Component.

Pass through the 600DAV FVZ types in Hauschild companiesIn with 2350 revs/min mixing 32.37g A- components and 7.67g B- components 2 minutes by two kinds of components so that obtain the adhesive that 40.0g are made.Here, such as existing By selected NH- equivalent weights to the 1 of epoxide equivalent weight in table 5:1 equivalent obtains 4.22 (A- components) 1 (B- of ratio Component) mixed proportion.

Table 5

And then after hybrid bonding agent formulation, described in the method for testing of following article, prepare test sample to determine to draw Stretch intensity, tensile shear strength and impact peel work(.According to three solidification patterns (4 hours 30 minutes at+60 DEG C at room temperature, 1 day at room temperature, at room temperature 7 days) solidification test sample after, determine the value provided in table 6.

Table 6

Tensile shear strength (ZSF) (DIN EN 1465)

By the embodiment adhesive composition and with the H380 for the electrogalvanising that size is 100x 25x 0.8mm Steel (EloZn) prepares sample.Here, bond area is 25x 10mm, thickness degree is 0.3mm.Draw speed is 10mm/min.

Impact peel work((ISO 11343)

By the embodiment adhesive composition and with the DC04 steel for the electrogalvanising that size is 90x 20x 0.8mm (EloZn) sample is prepared, is 20x 30mm in this bond area, thickness degree is 0.3mm.Respectively with three times at a temperature of providing The mode of determination carries out the measurement of impact peel work(.Impact velocity is 2m/s.Experiment curv (from 25 to 90%, according to ISO11343 the area below) provides the energy to failure (BE) represented with joule.

Tensile strength (ZF) (DIN EN ISO 527)

Adhesive sample is squeezed into 2mm thickness degree between two Teflon paper.Teflon paper is removed after solidification And according to DIN- standard state punching press samples.Sample is measured with 2mm/min draw speed under standard climate.According to DIN EN ISO 527 determine tensile strength.

Claims (22)

1. preparing the method for the liquid rubber of the impact modifier blocked comprising epoxide group, methods described includes making formula (II) Isocyanate-terminated prepolymer and at least one epoxy resin selected from acid anhydrides and aldehyde are used as glycol capturing agent at least one Compound in the presence of react

Wherein X₁=O, S or NH；

Y₁Represent n valency group of the reactive polymer after terminal amino group, sulfydryl or hydroxyl is removed；

Y₂The divalent group of aliphatic, alicyclic, aromatics or araliphatic diisocyanate after isocyanate groups are removed is represented, Or represent that the trimer or biuret of aliphatic, alicyclic, aromatics or araliphatic diisocyanate are removing isocyanate groups Trivalent radical afterwards；

M=1 or 2；With

N=2,3 or 4；

The epoxide with primary hydroxyl or secondary hydroxyl of the epoxy resin comprising formula (III)

Wherein Y₃Represent removing epoxy radicals comprising primary hydroxyl or the aliphatic, alicyclic of secondary hydroxyl, aromatics or araliphatic epoxides Group after group and primary hydroxyl or secondary hydroxyl；With

Q=1,2 or 3；

The isocyanate-terminated prepolymer, epoxy resin and glycol capturing agent of formula (II) is mixed with each other or make epoxy Resin reacts with glycol capturing agent, it is mixed with the isocyanate-terminated prepolymer of formula (II).

2. according to the method described in claim 1, it is characterised in that the n=2 or 3 in formula (II).

3. method according to claim 1 or 2, it is characterised in that the isocyanate-terminated prepolymer of formula (II) passes through With X₁The reaction of the prepolymer of H- groups and one or more polyisocyanates is obtained, described to carry X₁The prepolymer of H- groups Selected from PPG, polybutadiene polyol, PEPA, polycarbonate polyol, the polyethers of NH- end-blockings and its mixing Thing.

4. method according to claim 1 or 2, it is characterised in that epoxy resin is or comprising from least one ring The reaction product of oxide and at least one dihydric alcohol, trihydroxylic alcohol or higher level polyalcohol, or from epoxy resin and at least A kind of reaction product of single phenol.

5. method according to claim 1 or 2, it is characterised in that epoxy resin is selected from bisphenol-A-diglycidyl ether-production Thing, Bisphenol F-diglycidyl ether-product or bisphenol-A/F- diglycidyl ethers-product.

6. method according to claim 1 or 2, it is characterised in that the epoxide of formula (III) is selected from trihydroxy methyl third Alkane diglycidyl ether, the dimer of bisphenol-A-diglycidyl ether, the dimer of Bisphenol F-diglycidyl ether, bisphenol-A/F- The dimer of diglycidyl ether or its mixture.

7. method according to claim 1 or 2, it is characterised in that compound of the epoxy resin comprising formula (VI) is used as formula (III) epoxide

Wherein R is H or methyl independently of one another.

8. method according to claim 1 or 2, it is characterised in that glycol capturing agent is acid anhydrides.

9. method according to claim 8, it is characterised in that acid anhydrides is selected from least one cyclic carboxylic acids acid anhydride.

10. method according to claim 9, it is characterised in that the cyclic carboxylic acids acid anhydride is butanedioic acid, butanedioic acid derivative The acid anhydrides of thing, phthalic acid or phthalic acid derivatives.

11. method according to claim 1 or 2, it is characterised in that the isocyanate-terminated prepolymer of formula (II) it is different Cyanate group with the epoxide of formula (III) by reacting so as to by partly or completely totally-enclosed.

12. method according to claim 1 or 2, it is characterised in that the consumption of glycol capturing agent is in 0.25 to 3.00 weight In the range of amount %, with the gauge of epoxy resin.

13. method according to claim 12, it is characterised in that the glycol capturing agent is acid anhydrides.

14. method according to claim 1 or 2, it is characterised in that the isocyanate-terminated prepolymer of formula (II) passes through With X₁The reaction of the prepolymer of H- groups, one or more polyisocyanates and at least one polyhydric phenols is obtained.

15. method according to claim 1 or 2, it is characterised in that the isocyanate-terminated prepolymer of formula (II) passes through The reaction of at least two polyalcohols and one or more polyisocyanates is obtained, wherein using at least one PPG and extremely A kind of rubber of few OH- end-blockings is used as polyalcohol.

16. method according to claim 15, it is characterised in that the weight of the PPG and the OH- rubber blocked Amount ratio is 7:3 to 2:In the range of 8.

17. comprising epoxide group block impact modifier liquid rubber, the liquid rubber by according to claim 1 to Method described in 16 any one is obtained.

18. the purposes of liquid rubber according to claim 17, in one-component or bicomponent epoxy resin composition The impact flexibility of the cured epoxy matrix material of middle rise.

19. the purposes of liquid rubber according to claim 18, it is characterised in that one-component or the two component epoxy tree Oil/fat composition is one-component or bicomponent epoxy resin adhesive.

20. one-component or bicomponent epoxy resin composition, it includes at least one liquid rubber according to claim 17 Glue.

21. one-component according to claim 20 or bicomponent epoxy resin composition, it is included

A) at least one epoxy resin (A)；With

B) liquid rubber.

22. one-component or bicomponent epoxy resin composition according to claim 20 or 21, it is characterised in that the ring Epoxy resin composition is one-component or bicomponent epoxy resin adhesive.